The invention relates to novel sulphonylamino(thio)carbonyl compounds, to a number of processes and to novel intermediates for their preparation, and to their use as herbicides.
It is already known that certain sulphonylaminocarbonyl compounds, such as, for example, the compounds 4,5-dimethoxy-2-(2-methoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4,5-dimethoxy-2-(2,5-dimethoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4,5-diethoxy-2-(2,5-dimethoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one and N-(2,5-dimethoxy-phenylsulphonyl)-1,5-dimethyl-1H-pyrazole-3-carbox-amide possess herbicidal properties (cf. EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266, DE 4029753). The action of these compounds, however, is not in every respect satisfactory.
The novel sulphonylamino(thio)carbonyl compounds have now been found of the general formula (I), 
in which
A represents a single bond, oxygen, sulphur or the group Nxe2x80x94R, in which R represents hydrogen, alkyl, alkenyl, alkinyl or cycloalkyl,
Q represents oxygen or sulphur,
R1 represents hydrogen or formyl or represents in each case optionally substituted alkyl, alkenyl, alkinyl, alkylcarbonyl, alkoxycarbonyl, alkylsulphonyl, cycloalkyl, cycloalkylcarbonyl or cycloalkylsulphonyl,
R2 represents cyano or halogen or represents in each case optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy or alkinyloxy, and
R3 represents in each case optionally substituted heterocyclyl having 5 ring members of which at least one is oxygen, sulphur or nitrogen and from one to three further ring members can be nitrogen,
and salts of compounds of the formula (I),
the previously known compounds 4,5-dimethoxy-2-(2,5-dimethoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4,5-diethoxy-2-(2,5-dimethoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one and N-(2,5-dimethoxy-phenylsulphonyl)-1,5-dimethyl-1H-pyrazole-3-carboxamiide being excluded by disclaimer.
The novel sulphonylamino(thio)carbonyl compounds of the general formula (I) are obtained if
(a) aminosulphonyl compounds of the general formula (II) 
xe2x80x83in which
A, R1 and R2 have the meanings given above
are reacted with (thio)carboxylic acid derivatives of the general formula (III) 
xe2x80x83in which
Q and R3 have the meanings given above and
z represents halogen, alkoxy, aryloxy or arylalkoxy,
optionally in the presence of an acid acceptor and optionally in the presence of a diluent,
or if
(b) sulphonyl iso(thio)cyanates of the general formula (I) 
xe2x80x83in which
A, Q, R1 and R2 have the meanings given above
are reacted with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3 has the meaning given above,
optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent,
or if
(c) chlorosulphonyl compounds of the general formula (VI) 
xe2x80x83in which
A, R1 and R2 have the meanings given above
are reacted with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3 has the meaning given above
and metal (thio)cyanates of the general formula (VII)
MQCNxe2x80x83xe2x80x83(VII)
xe2x80x83in which
Q has the meaning given above, and
M represents an alkali metal or alkaline earth metal equivalent,
optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent,
or if
(d) chlorosulphonyl compounds of the general formula (VI) 
xe2x80x83in which
A, R1 and R2 have the meanings given above
are reacted with (thio)carboxamides of the general formula (VIII) 
xe2x80x83in which
Q and R3 have the meanings given above,
optionally in the presence of an acid acceptor and optionally in the presence of a diluent,
or if
(e) sulphonylamino(thio)carbonyl compounds of the general formula (IX) 
xe2x80x83in which
A, Q, R1 and R2 have the meanings given above, and
Z represents halogen, alkoxy, aryloxy or arylalkoxy,
are reacted with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3 has the meaning given above,
optionally in the presence of an acid acceptor and optionally in the presence of a diluent,
or if
(f) heterocycles of the general formula (V)
Hxe2x80x94R3xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3 has the meaning given above,
are reacted with chlorosulphonyl iso(thio)cyanate, optionally in the presence of a diluent, and the adducts formed in this reaction are reacted in situ with benzene derivatives of the general formula (X) 
xe2x80x83in which
A, R1 and R2 have the meanings given above,
optionally in the presence of an acid acceptor and optionally in the presence of a diluent,
and, if desired, the compounds of the formula (I) obtained by processes (a), (b), (c), (d), (e) or (f) are converted into salts by customary methods.
The novel sulphonylamino(thio)carbonyl compounds of the general formula (I) are distinguished by a strong herbicidal activity.
The invention relates preferably to compounds of the formula (I) in which
A represents a single bond, oxygen, sulphur or the group Nxe2x80x94R, in which R represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl or C3-C6-cycloalkyl,
Q represents oxygen or sulphur,
R1 represents hydrogen or formyl or represents in each case optionally cyano-, fluoro-, chloro-, bromo-, phenyl- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkylcarbonyl, alkoxycarbonyl or alkylsulphonyl having in each case up to 6 carbon atoms, or represents in each case optionally cyano-, fluoro-, chloro-, bromo- or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyl-carbonyl or C3-C6-cycloalkyl-sulphonyl,
R2 represents cyano, fluoro, chloro or bromo or represents in each case optionally cyano-, fluoro-, chloro-, bromo- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy or alkinyloxy having in each case up to 6 carbon atoms, and
R3 represents in each case optionally substituted heterocyclyl of the formulae below, 
xe2x80x83in which
Q1, Q2 and Q3 each represent oxygen or sulphur, and
R4 represents hydrogen, hydroxyl, amino or cyano, or represents C2-C10-alkylideneamino, or represents optionally fluoro-, chloro-, bromo-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, or represents in each case optionally fluoro-, chloro- and/or bromo-substituted C2-C6-alkenyl or C2-C6-alkinyl, or represents in each case optionally fluoro-, chloro-, bromo-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylamino or C1-C6-alkyl-carbonylamino, or represents C3-C6-alkenyloxy, or represents di-(C1-C4-alkyl)-amino, or represents in each case optionally fluoro-, chloro-, bromo-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkylamino or C3-C6-cycloalkyl-C1-C4-alkyl, or represents in each case optionally fluoro-, chloro-, bromo-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- and/or C1-C4-alkoxy-substituted phenyl, phenylamino or phenyl-C1-C4-alkyl,
R5 represents hydrogen, hydroxyl, mercapto, amino, cyano, fluoro, chloro, bromo or iodo, or represents optionally fluoro-, chloro-, bromo-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, or represents in each case optionally fluoro-, chloro- and/or bromo-substituted C2-C6-alkenyl or C2-C6-alkinyl, or represents in each case optionally fluoro-, chloro-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylthio, C1-C6alkylamino or C1-C6-alkyl-carbonylamino, or represents C3-C6-alkenyloxy, C3-C6-alkinyloxy, C3-C6-alkenylthio, C3-C6-alkinylthio, C3-C6-alkenylamino or C3-C6-alkinylamino, or represents di-(C1-C4-alkyl)-amino, or represents in each case optionally methyl- and/or ethyl-substituted aziridino, pyrrolidino, piperidino or morpholino, or represents in each case optionally fluoro-, chloro-, bromo-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-C6-cycloalkylamino C3-C6-cycloalkyl-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkoxy, C3-C6-cycloalkyl-C1-C4-alkylthio or C3-C6-cycloalkyl-C1-C4-alkylamino, or represents in each case optionally fluoro-, chloro-, bromo-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl-, C1-C4-alkoxy- and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyl-C1-C4-alkyl, phenoxy, phenyl-C1-C4-alkoxy, phenylthio, phenyl-C1-C4-alkylthio, phenylamino or phenyl-C1-C4-alkylamino, or
R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and also
R6, R7 and R8 are identical or different and represent hydrogen, cyano, fluoro, chloro or bromo, or represent in each case optionally fluoro-, chloro-, bromo- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylsulphinyl and alkylsulphonyl having in each case up to 6 carbon atoms, or represents in each case optionally cyano-, fluoro-, chloro-, bromo- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,
the previously known compounds 4,5-dimethoxy-2-(2,5-dimethoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4,5-diethoxy-2-(2,5-dimethoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one and N-(2,5-dimethoxy-phenylsulphonyl)-1,5-dimethyl-1H-pyrazole-3-carboxamide being excluded by disclaimer.
The invention also relates preferably to sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-ammonium, tetra-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-sulphonium, C5- or C6-cycloalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I) in which A, Q, R1, R2 and R3 have the meanings indicated above as preferred.
The invention relates in particular to compounds of the formula (I) in which
A represents a single bond, oxygen or the group Nxe2x80x94R, in which R represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propinyl, butinyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
Q represents oxygen or sulphur,
R1 represents hydrogen or formyl, or represents in each case optionally fluoro-, chloro-, bromo-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propinyl, butinyl, acetyl, propionyl, butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, n-, i-, s- or t-butylsulphonyl, or represents in each case optionally fluoro-, chloro- or methyl-substituted cyclopropyl, cyclopropylcarbonyl or cyclopropylsulphonyl,
R2 represents cyano, fluoro, chloro or bromo, or represents in each case optionally fluoro-, chloro-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propinyl, butinyl, methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy, butenyloxy, propinyloxy or butinyloxy and
R3 represents in each case optionally substituted heterocyclyl of the formulae below, 
xe2x80x83in which
Q1, Q2 and Q3 each represent oxygen or sulphur, and
R4 represents hydrogen, hydroxyl or amino, or represents C3-C8-alkyli-deneamino, or represents in each case optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally fluoro-, chloro- or bromo-substituted propenyl, butenyl, propinyl or butinyl, or represents in each case optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, or represents propenyloxy or butenyloxy, or represents dimethylamino or diethylamino, or represents in each case optionally fluoro-, chloro-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents in each case optionally fluoro-, chloro-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl,
R5 represents hydrogen, hydroxyl, mercapto, amino, fluoro, chloro or bromo, or represents in each case optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally fluoro-, chloro- or bromo-substituted ethenyl, propenyl, butenyl, propinyl or butinyl, or represents in each case optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, or represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, propadienylthio, butenylthio, propinylthio, butinylthio, propenylamino, butenylamino, propinylamino or butinylamino, or represents dimethylamino, diethylamino or dipropylamino, or represents in each case optionally fluoro-, chloro-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or represents in each case optionally fluoro-, chloro-, methyl-, trifluoromethyl-, methoxy- and/or methoxy-carbonyl substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or
R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and also
R6, R7 and R8 are identical or different and represent hydrogen, cyano, fluoro, chloro or bromo, or represent in each case optionally fluoro-, chloro-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl, propinyl, butinyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, propenytoxy, butenyloxy, propinyloxy, butinyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio, butinylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, or represent cyclopropyl,
the previously known compounds 4,5-dimethoxy-2-(2,5-dimethoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, 4,5-diethoxy-2-(2,5-dimethoxy-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one and N-(2,5-dimethoxy-phenylsulphonyl)-1,5-dimethyl-1H-pyrazole-3-carboxamide being excluded by disclaimer.
A very particularly preferred group of compounds according to the invention are the compounds of the formula (I), in which
A represents a single bond,
Q represents oxygen or sulphur,
R1 represents methyl, ethyl, n- or i-propyl,
R2 represents chloro or methyl- in each case in position 5 or 6- and
R3 represents optionally substituted triazolinyl of the formula below 
xe2x80x83in which
Q1 represents oxygen or sulphur, and
R4 represents in each case optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents propenyl or a propinyl, or represents methoxy, ethoxy, n- or i-propoxy, or represents cyclopropyl, and
R5 represents hydrogen, chloro or bromo, or represents in each case optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents in each case optionally fluoro and/or chloro-substituted propenyl or propinyl, or represents in each case optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, or represents propenyloxy or cyclopropyl.
The radical definitions listed above, whether general or listed in ranges of preference, apply not only to the end products of the formula (I) but also, correspondingly, to the starting materials and/or intermediates required in each case of the preparation. These radical definitions can be combined as desired with one another, thus including combinations between the preferred ranges indicated.
Using, for example, 2-fluoro-6-methoxy-benzenesulphonamide and 5-ethoxy-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazole-3-thione as starting materials, the course of reaction in the process (a) according to the invention can be illustrated by the following equation: 
Using, for example, 2-ethoxy-6-methyl-phenylsulphonyl-isothiocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of reaction in the process (b) according to the invention can be illustrated by the following equation: 
Using, for example, 2-methoxy-3-methyl-benzenesulphochloride, 5-ethylthio-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one and potassium cyanate as starting materials, the course of reaction in the process (c) according to the invention can be illustrated by the following equation: 
Using, for example, 2-ethoxy-4-fluoro-benzenesulphochloride and 5-methyl-1,2,4-oxadiazole-3-carboxamide as starting materials, the course of reaction in the process (d) according to the invention can be illustrated by the following equation: 
Using, for example, N-(2-chloro-6-propoxy-phenylsulphonyl)-O-methyl-urethane and 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of reaction in the process (e) according to the invention can be illustrated by the following equation: 
Using, for example, 5-chloro-4-ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one and chlorosulphonylisocyanate and then 2-ethoxy-6-methyl-aniline as starting materials, the course of reaction in the process (f) according to the invention can be illustrated by the following equation: 
A general definition of the aminosulphonyl compounds to be used as starting materials in the process (a) according to the invention for the preparation of compounds of the formula (I) is given by the formula (II). In the formula (II) A, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared in accordance with the invention, as being preferable or, respectively, particularly preferable for A, R1 and R2.
The starting materials of the formula (II) are known and/or can be prepared by methods known per se (cf. EP 216504, DE 3208189, EP 44807, EP 23422).
Compounds not yet known from the literature, and which as novel substances are likewise a subject of the present application, are the sulphonamides of the general formula (IIa), 
in which
A1 represents ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, trifluoroethyl, chlorotrifluoroethyl, methoxyethyl, ethoxyethyl, allyl, propargyl or benzyl, and
A2 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl.
The novel sulphonamides of the formula (IIa) are obtained if sulphonyl chlorides of the formula (VIa) 
in which
A1 and A2 have the meanings given above
are reacted with ammonia, optionally in the presence of a diluent, for example water, at temperatures between 0xc2x0 C. and 50xc2x0 C. (cf. the Preparation Examples).
The starting materials of the formula (II) can in general be obtained also by reacting phenol derivatives of the formula (IIb) 
in which
A and R2 have the meanings given above
with alkylating agents of the formula (XI)
Xxe2x80x94R1xe2x80x83xe2x80x83(XI)
xe2x80x83in which
R1 has the meaning given above, and
X represents halogen or the group R1xe2x80x94Oxe2x80x94SO2xe2x80x94Oxe2x80x94,
optionally in the presence of an acid acceptor, for example potassium carbonate, and optionally in the presence of a diluent for example toluene, at temperatures between 10xc2x0 C. and 150xc2x0 C. (cf. the Preparation Examples).
The phenol derivatives of the formula (IIb) required as precursors are known and/or can be prepared by methods known per se (cf EP 44807, Metalloberflxc3xa4che [Metal surface]xe2x80x94Angew. Elektrochernie 27 (1973), 217-227xe2x80x94cited in Chemn. Abstracts 79:86733; Preparation Examples).
The alkylating agents of the formula (XI) which are also required as precursors are known synthesis chemicals.
A general definition of the (thio)carboxylic acid derivatives also to be used as starting materials in the process (a) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (III). In the formula (III), Q and R3 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared in accordance with the invention, as being preferable or, respectively, particularly preferable for Q and R3; Z preferably represents fluorine, chlorine, bromine, C1-C4-alkoxy, phenoxy or benzyloxy, and in particular represents chlorine, methoxy, ethoxy or phenoxy.
The starting materials of the formula (III) are known and/or can be prepared by methods known per se (cf. EP 459244, EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266).
A general definition of the sulphonyl iso(thio)cyanate to be used as starting materials in the process (b) according to the invention for the preparation of the compounds of the formula (I) is given with the formula (IV). In the formula (IV), A, Q, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared in accordance with the invention, as being preferable or particularly preferable for A, Q, R1 and R2.
The starting materials of the formula (IV) are known and/or can be prepared by methods known per se (cf. EP 23422, EP 216504).
Compounds not yet known from the literature, and which as novel substances are likewise a subject of the present application, are the sulphonyl iso(thio)cyanates of the general formula (IVa) 
in which
Q represents oxygen or sulphur,
A1 represents ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, trifluoroethyl, chlorotrifluoroethyl, methoxyethyl, ethoxyethyl, allyl, propargyl or benzyl, and
A2 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl.
The novel sulphonyl iso(thio)cyanates of the formula (IVa) are obtained if sulphonamides of the formula (IIa)xe2x80x94abovexe2x80x94are reacted with phosgene or, respectively, thiophosgene, optionally in the presence of an alkyl isocyanate, for example butyl isocyanate, optionally in the presence of a reaction auxiliary, for example diazabicyclo[2.2.2]octane, and in the presence of a diluent, for example toluene, xylene or chlorobenzene, at temperatures between 80xc2x0 C. and 150xc2x0 C., and, after the end of the reaction, the volatile components are distilled off under reduced pressure.
A general definition of the heterocycles also to be used as starting materials in the processes (b), (c), (e) and (f) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (V). In the formula (V), R3 preferably or in particular has that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared in accordance with the invention, as being preferable or particularly preferable for R3.
The starting materials of the formula (V) are known and/or can be prepared by methods known per se (cf EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266).
A general definition of the chlorosulphonyl compounds to be used as starting materials in the processes (c) and (d) according to the invention for the preparation of compounds of the formula (I) is given by the formula (VI). In the formula (VI), A, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared in accordance with the invention, as being preferable or particularly preferable for A, R1 and R2.
The starting materials of the formula (VI) are known and/or can be prepared by methods known per se (cf. EP 511826, DE 3208189, EP23422).
Compounds not yet known from the literature, which as novel substances are likewise a subject of the present application, are the sulphonyl chlorides of the formula (VIa) 
in which
A1 represents ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, trifluoroethyl, chlorotrifluoroethyl, methoxyethyl, ethoxyethyl, allyl, propargyl or benzyl, and
A2 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl.
The novel sulphonyl chlorides of the formula (VIa) are obtained if aniline derivatives of the formula (XII) 
in which
A1 and A2 have the meanings given above
are reacted with an alkali metal nitrite, for example sodium nitrite, in the presence if hydrochloric acid at temperatures between xe2x88x9210xc2x0 C. and +10xc2x0 C., and the diazonium salt solution thus obtained is reacted with sulphur dioxide in the presence of a diluent, for example dichloromethane or 1,2-dichloro-ethane, and in the presence of a catalyst, for example copper(I) chloride, optionally in the presence of a further catalyst, for example dodecyltrimethylammonium bromide, at temperatures between xe2x88x9210xc2x0 C. and +50xc2x0 C. (cf. the Preparation Examples).
The aniline derivatives of the formula (XII) required as precursors are known and/or can be prepared by methods known per se (cf. EP 511826, U.S. Pat. No. 4,992,091, EP 185128, DE 2405479, Preparation Examples).
The abovementioned novel benzenesulphonic acid derivatives of the formulae (IIa), (IVa) and (VIa) can be defined comprehensively by the following formula (XIII): 
in which
E represents xe2x80x94NH2, xe2x80x94Nxe2x95x90Cxe2x95x90Q or xe2x80x94Cl, where
Q represents O or S, and also
A1 represents ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, trifluoroethy, chlorotrifluoroethyl, methoxyethyl, ethoxyethyl, allyl, propargyl or benzyl, and
A2 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl.
A general definition of the (thio)carboxamides to be used as starting materials in the process (d) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (VIII). In the formula (VIII), Q and R3 preferably or in particular have that meaning which has already been indicated above, in connection with a description of the compounds of the formula (I) to be prepared in accordance with the invention, as being preferable or particularly preferable for Q and R3.
The starting materials of the formula (VIII) are known and/or can be prepared by methods known per se (cf. EP 459244).
A general definition of the sulphonylamino(thio)carbonyl compounds to be used as starting materials in the process (e) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (IX). In the formula (IX), A, Q, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared in accordance with the invention, as being preferable or particularly preferable for A, Q, R1 and R2; Z preferably represents fluoro, chloro, bromo, C1-C4-alkoxy, phenoxy or benzyloxy, and in particular represents chlorine, methoxy, ethoxy or phenoxy.
A general definition of the benzene derivatives to be used as starting materials in the process (f) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (X). In the formula (X), A, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared in accordance with the invention, as being preferable or particularly preferable for A, R1 and R2.
Starting materials of the formula (X) are known and/or can be prepared by methods known per se (cf. EP 511826, U.S. Pat. No. 4,992,091, EP 185128, DE 2405479, Preparation Examples).
The processes (a), (b), (c), (d), (e) and (f) according to the invention for the preparation of the novel compounds of the formula (I) are preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and o-dichlorobenzene; ethers such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxanes; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; esters such as methyl acetate and ethyl acetate; nitrites, for example acetonitrile and propionitrile; amides, for example dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide.
As reaction auxiliaries and/or as acid acceptors in the processes (a), (b), (c), (d), (e) and (f) according to the invention it is possible to employ all acid-binding agents which can customarily be used for such reactions. Preferred among suitable examples are alkali metal hydroxides, for example sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, for example calcium hydroxide, alkali metal carbonates and alcoholates, such as sodium carbonate and potassium carbonate, sodium tert-butylate and potassium tert-butylate, and also basic nitrogen compounds; such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2.2.2]-octane (DABCO).
The reaction temperatures in the processes (a), (b), (c), (d), (e) and (f) according to the invention can be varied within a relatively wide range. They are in general carried out at temperatures of between xe2x88x9220xc2x0 C. and +150xc2x0 C., preferably at temperatures between 0xc2x0 C. and +100xc2x0 C.
The processes (a), (b), (c), (d), (e) and (f) according to the invention are generally carried out under atmospheric pressure. However it is also possible to operate under increased or reduced pressure.
For carrying out processes (a), (b), (c), (d), (e) and (f) according to the invention, the starting materials required in each case are in general employed in approximately equimolar quantities. However, it is also possible to use one of the components employed in each case in a relatively large excess. The reactions are in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a number of hours at the particular temperature required. Working up in the case of the processes (a), (b), (c), (d), (e) and (f) according to the invention is in each case by customary methods (cf the Preparation Examples).
Salts of the compounds of the general formula (I) according to the invention can be prepared if desired. Such salts are obtained in a simple manner by customary methods of forming salts, for example by dissolving or dispersing a compound of the formula (I) in an appropriate solvent, for example methylene chloride, acetone, tert-butyl methyl ether or toluene, and adding an appropriate base. The salts can thenxe2x80x94if desired after prolonged stirringxe2x80x94be isolated by concentration or filtration with suction.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.
The compounds of the formula (I) according to the invention are preferably suitable for combating monoctyledon and dicotyledon broad-leaved weeds, both pre-emergence and post-emergence. They exhibit strong herbicidal activity and a broad spectrum action when used on the soil and on above-ground parts of the plants.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
As solid carriers there are suitable:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methyl cellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example anilides, for example diflufenican and propanil; arylcarboxylic acids, for example dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, for example 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, for example diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones, for example chloridazon and norflurazon; carbamates, for example chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides, for example alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines, for example oryzalin, pendimethalin and trifluralin; diphenyl ethers, for example acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas, for example chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines, for example alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, for example imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, for example bromoxynil, dichlobenil and ioxynil; oxyacetamides, for example mefenacet; sulphonyl-ureas, for example amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates, for example butylate, cycloate, diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, for example atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones, for example hexazinone, metamitron and metribuzin; others, for example aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.